1. Field of the Invention
The present invention relates to a method for producing a new allyl compound different from an allyl starting material compound by reacting the allyl starting material compound with an oxygen nucleophilic agent in the presence of a catalyst, and an ether or ester compound produced thereby.
2. Prior Arts
Various kinds of new allyl compounds can be synthesized by carrying out a catalytic reaction using a transition metal compound and using an allyl compound as a starting material. This reaction proceeds as illustrated in the following reaction formula, wherein an allyl starting material compound having an eliminating group X is π-coordinated and oxidatively added to a transition metal compound to form a π-allyl complex having three carbons of the allyl part bonded to a metal and the terminal allyl carbon of the π-allyl complex is attacked by a nucleophilic agent expressed by Nu—H or Nu−.

The synthesizing reaction of an allyl compound is generally fully described in “Palladium Reagents and Catalysts -Innovations in Organic Synthesis-” published by John Wiley & Sons Company, and various products in a form of allylated nucleophilic agent can be obtained by electing a kind of a nucleophilic agent in the reaction. Among them, when the nucleophilic agent is an oxygen nucleophilic agent such as alcohols, phenols, or carboxylic acids, respective allyl alkyl ether, allyl phenyl ether or allyl carboxylate esters are synthesized, and they are considered to be one of basic reactions useful in synthetic chemistry.
However, as a reaction example of an allyl starting material compound and an oxygen nucleophilic agent, the case in which the oxygen nucleophilic agent is carboxylic acid anion, is generally well known, but there are not so many reaction examples with other oxygen nucleophilic agents due to their low reactivity.
For example, as described in “Organometallics, 1995, 14, p. 4585” illustrating a reaction example with phenols, a synthesis example of allyl phenyl ethers by a palladium catalyst system having a triaryl type monodentate phosphite ligand such as triphenyl phosphite is well known, but its activity is not sufficient.
Also, reaction examples with alcohols are very limited due to low nucleophilic attacking property of alcohol oxygen. As a reaction example between molecules of alcohol oxygen and an allyl starting material compound, dehydration condensation reaction of an allyl alcohol by a catalyst system using a monodentate phosphite ligand of triphenyl phosphite or triethyl phosphite was reported in “Nihon Kagakukai Kouen Yokoushuu, 2001, Vol. 79th, No. 2, p. 1194” and “Nihon Gakujutsu Shinkoukai Souzou Kinou Kagaku Dai 116 Iinkai 2002, 6, Godou Bunkakai Shiryou p. 46”. Also, a reaction of alcohols with an allyl alcohol by a catalyst system comprising triphenylphosphite considered to have a highest activity was also reported. However, its catalyst activity is still not high.
As an example of attacking a π-allyl complex by other alcohol oxygen, there are known some cyclizing reactions wherein the cyclization is carried out intramolecularly by attacking π-allyl terminal carbon with alcohol oxygen present at such a position as to form a 5-membered ring or a 6-membered ring in the reaction process. For example, as described in “Tetrahedron Lett., 1995, 36, p. 5527”, there is known a synthesis example of a morpholine derivative by a palladium catalyst system having triisopropyl phosphite as a monodentate phosphite ligand. Also, a synthesis example of a 5-membered cyclic product by a palladium catalyst system having a bidentate phosphite ligand having cyclic both terminals composed of a pentan-2,5-diyl group was reported in “J. Am. Chem. Soc., 1998, 120, p. 1732”. However, it is necessary for these reactions that an oxygen nucleophilic agent is present at such a position as to easily form a ring, and they are allylation reaction which can proceed only intramolecularly and which is a special system.
When carrying out allylation reaction using the above-mentioned catalyst on an industrial scale, it is strongly demanded to improve a reactivity in order to reduce an amount of expensive palladium used, which is a noble metal, or to make a reactor size smaller, thereby reducing a manufacturing cost. As a method for improving the reactivity, there is a method for having a counter cation of a nucleophilic agent present in the reaction system. As its effect, a nucleophilic agent forming a pair or a coexistent state with such a counter cation increases its nucleophilic attacking force, thereby improving the reactivity.
As some examples, a reaction of cyclopentadiene monoxide and an acetic acid anion is reported in “Organic Syntheses, 1998, 67, p114”, and in order to improve the reactivity, a sodium ion is used as a counter cation for acetic anion in this reaction. However, when such an alkali metal is a counter cation, +1 valent charge is concentrated on one small metal ion, and accordingly there is a tendency of forming a strong ion pair with a nucleophilic agent of a counter anion. Consequently, the attacking force of such a nucleophilic agent is not sufficiently high.
For example, it is reported in “Tetrahedron Lett., 1998, 39, p5439” that an allyl starting material compound and a formic acid anion are reacted by using a palladium catalyst comprising a triisopropyl phosphite ligand of trialkyl type monodentate phosphite in the presence of ammonium comprising triethylamine having a proton coordinate-bonded, but this reaction is a reaction different from a reaction of an ordinary allyl starting material compound and a nucleophilic agent. That is, the formic acid anion does not form allyl formate by attacking a π-allyl complex as an intermediate but is coordinated to palladium, and carbon dioxide is eliminated and a hydride formed as this result reacts with the π-allyl complex to provide a product of a structure having the allyl starting material reduced.
As mentioned above, although it is possible to produce ether compounds or ester compounds important in organic synthesis by their reaction of an allyl starting material compound and its different oxygen nucleophilic agent, a highly active catalyst system which can sufficiently react an oxygen nucleophilic agent having a low reactivity has not been developed, and therefore practical reaction examples are actually limited. Particularly, in the reaction with alcohols, it is impossible to sufficiently proceed the reaction unless a special environment such as the above-mentioned intramolecular cyclization reaction is provided. Therefore, it has been demanded to develop a new catalyst system which achieves a sufficiently high catalyst activity even in the reaction with such an oxygen nucleophilic agent as having a low reactivity.
The present invention has been made for solving the above-mentioned problems. Thus, an object of the present invention is to provide a method for producing an allyl compound, which can efficiently produce various allyl compounds by using a new catalyst system achieving an especially high activity to such an oxygen nucleophilic agent as having a low reactivity in the reaction of an allyl starting material compound and an oxygen nucleophilic agent, and to provide an ether compound and an ester compound.
The present inventors have intensively studied to develop a catalyst system capable of efficiently proceeding a reaction among molecules of various allyl starting material compounds and their different oxygen nucleophilic agents, and have discovered that a catalyst system comprising a multidentate phosphite compound and a transition metal compound of Group 8 to Group 10 of the Periodic Table achieves an unexpectedly very high activity as compared with a conventional catalyst system of monodentate phosphine or bidentate phosphine and a catalyst system of triphenyl phosphite known as a prior art. The present invention has been accomplished on the basis of this discovery.